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Electrochemically-aided control of solid phase micro-extraction (EASPME) using conducting polymer coated fiber.

机译:使用导电聚合物涂覆的纤维对固相微萃取(EASPME)进行电化学辅助控制。

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摘要

Conducting polymers represent a class of new materials that have electronic conductivity. Polyacetylene was the first polymer that could be made conductive. The first experiments were conducted in the mid 1970s, and since then a number of other conducting polymers have been synthesized. The most important polymers are polyacetylene, polypyrrole, polythiophene, and polyaniline.; Conducting polymer films can be doped when exposed to an aqueous solution containing an analyte ion at a particular oxidizing potential. The dopant may be expelled when the polymer film is reduced to its neutral form by applying a constant reduction potential for a period of time.; Chemical speciation becomes important for trace metal analysis. It is not sufficient to quantitate the total elemental content of the samples to define toxicities. The principal analyzed compounds for the speciation of arsenic are arsenate, arsenite, dimethylarsenic acid (DMA), and arsenobetaine [(CH3)3As+CH2COO- ] and these have varying toxicities. Therefore, for the proper evaluation of the risks associated with the exposure of biological systems to arsenic compounds speciation must be investigated.; Solid Phase Micro-Extraction (SPME) using fused silica fibers coated with liquid polymeric materials such as poly(dimethylsiloxane) (PDMS) has been found to be a very useful technique for preconcentration of anions from environmental aqueous media. To maximize the uptake two criteria must be satisfied: the interaction energy of the fiber system must be large and the coating must be thick. On the other hand, they result in both unfavorable desorption thermodynamics and slow desorption kinetics. Therefore, SPME sampling and desorption in particular, can take as long as hours to perform.; Electronically conducting polymers such as poly (3-methylthiophene) (P3MT), and poly(3,4-ethylenedioxythiophene) (PEDOT) form cation radicals in the polymer matrix upon electro-oxidation. The material thus becomes hydrophilic and swells as it adsorbs water. In addition, to maintain electroneutrality in the matrix, anionic counter ions must be taken up from the solution phase. On switching the applied potential to negative values the polymer is reduced to its neutral (uncharged) state. The polymer matrix becomes hydrophobic and has a negative potential. The previously incorporated anions rapidly are expelled from the polymer as a result of these two forces.
机译:导电聚合物代表了一类具有电子导电性的新材料。聚乙炔是第一种可以导电的聚合物。最初的实验是在1970年代中期进行的,此后便合成了许多其他导电聚合物。最重要的聚合物是聚乙炔,聚吡咯,聚噻吩和聚苯胺。当暴露于含有特定氧化电位的分析物离子的水溶液中时,可以对导电聚合物薄膜进行掺杂。当通过施加恒定的还原电位一段时间将聚合物膜还原成其中性形式时,可以将掺杂剂排出。化学形态对于痕量金属分析变得重要。仅定量样品中的总元素含量以定义毒性是不够的。用于分析砷形态的主要化合物为砷酸盐,亚砷酸盐,二甲基砷酸(DMA)和砷甜菜碱[(CH3)3As + CH2COO-],它们具有不同的毒性。因此,为了正确评估与生物系统接触砷化合物有关的风险,必须研究物种形成。已经发现,使用涂覆有液态聚合物材料(例如聚(二甲基硅氧烷)(PDMS))的熔融石英纤维进行的固相微萃取(SPME)是从环境水性介质中预浓缩阴离子的非常有用的技术。为了最大程度地吸收,必须满足两个条件:纤维系统的相互作用能必须大,涂层必须厚。另一方面,它们导致不利的解吸热力学和缓慢的解吸动力学。因此,特别是SPME采样和解吸可能要花费长达几个小时的时间。诸如聚(3-甲基噻吩)(P3MT)和聚(3,4-乙撑二氧噻吩)(PEDOT)之类的导电聚合物在电氧化后会在聚合物基质中形成阳离子自由基。因此,该材料变得亲水并在吸收水时溶胀。另外,为了保持基质中的电子中性,必须从溶液相吸收阴离子抗衡离子。在将施加的电势切换为负值时,聚合物还原为中性(不带电)状态。聚合物基质变为疏水性并具有负电势。由于这两个力,先前结合的阴离子迅速从聚合物中排出。

著录项

  • 作者

    Ceylan, Ozcan.;

  • 作者单位

    University of Cincinnati.;

  • 授予单位 University of Cincinnati.;
  • 学科 Chemistry Analytical.
  • 学位 Ph.D.
  • 年度 2003
  • 页码 100 p.
  • 总页数 100
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;
  • 关键词

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